CN113121796B - Preparation method of low-dielectric silicon amine-epoxy resin copolymer - Google Patents
Preparation method of low-dielectric silicon amine-epoxy resin copolymer Download PDFInfo
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- CN113121796B CN113121796B CN202110507327.8A CN202110507327A CN113121796B CN 113121796 B CN113121796 B CN 113121796B CN 202110507327 A CN202110507327 A CN 202110507327A CN 113121796 B CN113121796 B CN 113121796B
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- amine
- ethyl
- phenyl
- methylenebis
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 silicon amine Chemical class 0.000 claims abstract description 57
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 34
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 33
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 26
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 8
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 8
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 8
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- OXEZLYIDQPBCBB-UHFFFAOYSA-N 4-(3-piperidin-4-ylpropyl)piperidine Chemical compound C1CNCCC1CCCC1CCNCC1 OXEZLYIDQPBCBB-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 5
- JJNMWNOFPKVUAV-UHFFFAOYSA-N CC(C)(C)[Si](C)(C)N1CCC(CCCC(CC2)CCN2[Si](C)(C)C(C)(C)C)CC1 Chemical compound CC(C)(C)[Si](C)(C)N1CCC(CCCC(CC2)CCN2[Si](C)(C)C(C)(C)C)CC1 JJNMWNOFPKVUAV-UHFFFAOYSA-N 0.000 claims description 4
- WPGQYYNVZKEQFW-UHFFFAOYSA-N C[Si](C)(C)N1CCC(CCCC(CC2)CCN2[Si](C)(C)C)CC1 Chemical compound C[Si](C)(C)N1CCC(CCCC(CC2)CCN2[Si](C)(C)C)CC1 WPGQYYNVZKEQFW-UHFFFAOYSA-N 0.000 claims description 4
- MUJJOOGPQAOXSG-UHFFFAOYSA-N C[Si](C)(C1=CC=CC=C1)N1CCC(CCCC(CC2)CCN2[Si](C)(C)C2=CC=CC=C2)CC1 Chemical compound C[Si](C)(C1=CC=CC=C1)N1CCC(CCCC(CC2)CCN2[Si](C)(C)C2=CC=CC=C2)CC1 MUJJOOGPQAOXSG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- SERBIEGEXHNUIU-UHFFFAOYSA-N CN(CCN(C)[Si](C)(C)C1=CC=CC=C1)[Si](C)(C)C1=CC=CC=C1 Chemical compound CN(CCN(C)[Si](C)(C)C1=CC=CC=C1)[Si](C)(C)C1=CC=CC=C1 SERBIEGEXHNUIU-UHFFFAOYSA-N 0.000 claims description 3
- XEYDLRDMKBYLSO-UHFFFAOYSA-N [4-[dimethyl(phenyl)silyl]piperazin-1-yl]-dimethyl-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C)N(CC1)CCN1[Si](C)(C)C1=CC=CC=C1 XEYDLRDMKBYLSO-UHFFFAOYSA-N 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- GRHVMNXJECNYQT-UHFFFAOYSA-N n-[tert-butyl(dimethyl)silyl]-n-methylaniline Chemical compound CC(C)(C)[Si](C)(C)N(C)C1=CC=CC=C1 GRHVMNXJECNYQT-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 150000003510 tertiary aliphatic amines Chemical class 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- XUTHRJJZMHXMFR-UHFFFAOYSA-N 4-(piperidin-4-ylmethyl)piperidine Chemical compound C1CNCCC1CC1CCNCC1 XUTHRJJZMHXMFR-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- LUZXFCNMHQMIBH-UHFFFAOYSA-N n-methyl-n-trimethylsilylaniline Chemical compound C[Si](C)(C)N(C)C1=CC=CC=C1 LUZXFCNMHQMIBH-UHFFFAOYSA-N 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 74
- 229920000642 polymer Polymers 0.000 description 27
- 239000000047 product Substances 0.000 description 26
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 230000001588 bifunctional effect Effects 0.000 description 12
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000012776 electronic material Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- HAHCAOMFKGXUGI-UHFFFAOYSA-N CN(C1=CC=C(CC(C=C2)=CC=C2N(C)[Si](C)(C)C)C=C1)[Si](C)(C)C Chemical compound CN(C1=CC=C(CC(C=C2)=CC=C2N(C)[Si](C)(C)C)C=C1)[Si](C)(C)C HAHCAOMFKGXUGI-UHFFFAOYSA-N 0.000 description 3
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical group CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 3
- 125000004193 piperazinyl group Chemical group 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- LFYWXCLUHWJVBW-UHFFFAOYSA-N CC(C)(C)[Si](C)(C)N(C)CCN(C)[Si](C)(C)C(C)(C)C Chemical compound CC(C)(C)[Si](C)(C)N(C)CCN(C)[Si](C)(C)C(C)(C)C LFYWXCLUHWJVBW-UHFFFAOYSA-N 0.000 description 2
- RJXHSBLJTFIDKM-UHFFFAOYSA-N CN(C1=CC=CC=C1)C(C=CC(CC(C=C1)=CC([SiH](C)C)=C1N(C)C1=CC=CC=C1)=C1)=C1[SiH](C)C Chemical compound CN(C1=CC=CC=C1)C(C=CC(CC(C=C1)=CC([SiH](C)C)=C1N(C)C1=CC=CC=C1)=C1)=C1[SiH](C)C RJXHSBLJTFIDKM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WQNZKMJHQBIKKO-UHFFFAOYSA-N n,n'-dimethyl-n,n'-bis(trimethylsilyl)ethane-1,2-diamine Chemical compound C[Si](C)(C)N(C)CCN(C)[Si](C)(C)C WQNZKMJHQBIKKO-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 101150032357 psaE gene Proteins 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RGPIMAKTKGQWEG-UHFFFAOYSA-N tert-butyl-[4-[tert-butyl(dimethyl)silyl]piperazin-1-yl]-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)N1CCN([Si](C)(C)C(C)(C)C)CC1 RGPIMAKTKGQWEG-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- DXEMNQJIDPYWPC-UHFFFAOYSA-N CN(C1=CC=CC=C1)C(C=CC=C1)=C1[SiH](C)C Chemical compound CN(C1=CC=CC=C1)C(C=CC=C1)=C1[SiH](C)C DXEMNQJIDPYWPC-UHFFFAOYSA-N 0.000 description 1
- MSQAXVYLHLQQIA-UHFFFAOYSA-N C[Si](C)(C1=CC=CC=C1)N1CCNCC1 Chemical compound C[Si](C)(C1=CC=CC=C1)N1CCNCC1 MSQAXVYLHLQQIA-UHFFFAOYSA-N 0.000 description 1
- FGSANRKDMXNQBI-UHFFFAOYSA-N C[Si](C)(C1=CC=CC=C1)NCCN Chemical compound C[Si](C)(C1=CC=CC=C1)NCCN FGSANRKDMXNQBI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JAYUTFFTIXDZLN-UHFFFAOYSA-N n'-[tert-butyl(dimethyl)silyl]ethane-1,2-diamine Chemical compound CC(C)(C)[Si](C)(C)NCCN JAYUTFFTIXDZLN-UHFFFAOYSA-N 0.000 description 1
- ZMVMYBGDGJLCHV-UHFFFAOYSA-N n-methyl-4-[[4-(methylamino)phenyl]methyl]aniline Chemical group C1=CC(NC)=CC=C1CC1=CC=C(NC)C=C1 ZMVMYBGDGJLCHV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AKFVXAJKYLBULF-UHFFFAOYSA-N tert-butyl-chlorosilyl-dimethylsilane Chemical group CC(C)(C)[Si](C)(C)[SiH2]Cl AKFVXAJKYLBULF-UHFFFAOYSA-N 0.000 description 1
- SUQBVXFGGATXQO-UHFFFAOYSA-N tert-butyl-dimethyl-piperazin-1-ylsilane Chemical compound CC(C)(C)[Si](C)(C)N1CCNCC1 SUQBVXFGGATXQO-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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Abstract
The invention discloses a preparation method of a low dielectric silicon amine-epoxy resin copolymer, belonging to the field of high molecular functional materials. The difunctional silicon amine-epoxy resin copolymer is obtained by adopting the difunctional silicon amine curing agent and the epoxy resin through the reaction processes of epoxy ring opening, silicon-based migration and the like under the catalysis of Lewis acid. The adopted difunctional silicon amine curing agent is synthesized by taking binary secondary amine and alkyl chlorosilane as raw materials. The difunctional silicon amine-epoxy copolymer prepared by the invention has outstanding low dielectric property, high mechanical property, thermal stability, hydrophobicity and other comprehensive properties.
Description
Technical Field
The invention belongs to the field of high molecular functional materials, and particularly relates to a preparation method of a low dielectric silicon amine-epoxy resin copolymer.
Background
The epoxy resin has the characteristics of good adhesion, high insulation, low shrinkage, good thermal stability, good molding manufacturability and the like, is widely applied to the fields of bonding materials of electronic components, packaging materials, printed circuit boards and the like, and is one of important electronic materials (J.Ind.Eng.chem.2015,29, 1-11; J.Mater.chem.C.2016,4, 5890-5906.). With the continuous development of high-speed high-frequency lines and communication technologies, the demand for high-frequency low-dielectric electronic materials is more urgent. High-frequency, high-speed, low dielectric materials need to satisfy low dielectric constant and low dielectric loss under high-frequency conditions to reduce signal transmission delay and crosstalk, and ensure reliability of signal transmission (mater.today 2006,9, 22-31; chem.rev.2010,110, 56-110.). Current epoxy resins for Electronic materials mainly use acid anhydride and aromatic amine as curing agents, but the curing reaction generates ester groups, hydroxyl groups, amine groups and the like with high polarity, resulting in high dielectric constant and dielectric loss (the acid anhydride cured epoxy resin epsilon >3, tan delta > 0.01; the amine cured epsilon is between 4 and 6, tan delta > 0.03), which cannot meet the application requirements of high-speed high-frequency Electronic circuits (Encapsulation Technologies for Electronic applications, Elsevier, 2018; ACS sustaineble chem.Eng.2018,6, 8856-. The low-dielectric polymer materials developed at present comprise polytetrafluoroethylene, polyimide, polyarylether, polybenzocyclobutene and the like, but the materials also have the defects of complex synthesis, harsh curing conditions, low adhesion, poor molding manufacturability and the like, and the application of the materials in the electronic material occasion is limited (Macromolecules 2019,52, 4601-4609; prog.Polym.Sci.,2010,35, 1022-1077; CN 106189087A). Therefore, the development of the novel low-dielectric epoxy resin electronic material has important theoretical significance and practical application value.
To reduce the dielectric constant and dielectric loss of the material, two strategies can be adopted: firstly, in the design of molecular structure, the polarizability of the molecule is reduced, namely the electric polarizability and the distortion polarizability of the molecule are reduced (mater. today 2004,7, 34-39.); the second is to increase the free volume ratio of the material to reduce the dipole number density (J.Am.chem.Soc.2003,125, 14113-14119). In recent years, it has become a current research focus to adopt a method of reducing polarizability and increasing a free volume ratio to obtain a low dielectric epoxy resin. The dielectric property of the epoxy resin can be improved to a certain extent by introducing C-F bonds (Eur.Polym.J.2018,100,96-102.), C-Si bonds (ACS Sustainable chem.Eng.2018,6,8856-8867.) or microporous structures (adv.Electron.Mater.2016,2,1500485-1500492.) into the epoxy resin. However, the methods do not change the curing mode of the epoxy resin, a large amount of polar groups such as hydroxyl groups, amino groups and the like are generated in the curing process, the problems of limited improvement of dielectric properties, particularly dielectric loss, incapability of accurately controlling a microporous structure, reduction of mechanical properties and the like exist, and the obtaining of the low-dielectric epoxy resin still has challenges.
Therefore, the development of a novel epoxy resin curing agent can inhibit the generation of polar groups such as hydroxyl or amino in the curing process, thereby realizing the low dielectric property of the epoxy resin, and having great significance for the development of novel low dielectric epoxy resin materials.
Disclosure of Invention
The invention aims to provide a preparation method of a low dielectric silicone amine-epoxy resin copolymer aiming at the defects and shortcomings of the prior art. The invention adopts difunctional silicon amine curing agent to copolymerize with epoxy resin to form silicon amine-epoxy copolymer. The difunctional silicon amine curing agent is characterized in that the generation of high-polarity groups such as hydroxyl, amino containing active hydrogen and the like in the epoxy polymerization process caused by a common curing agent is avoided through the reaction processes such as epoxy ring opening, silicon base migration and the like, the dielectric constant and the dielectric loss of a polymer can be obviously reduced, and the polymer material with low dielectric property is obtained. The synthesis method of the bifunctional silicon amine curing agent adopts diamine and alkyl chlorosilane as raw materials, obtains the bifunctional silicon amine curing agent through nucleophilic substitution reaction under the action of alkali and through reduced pressure distillation-solvent extraction, separation and purification, and can be used as the curing agent of epoxy resin, and the obtained bifunctional silicon amine-epoxy copolymer shows excellent comprehensive properties such as low dielectric property, mechanical property, thermal stability, hydrophobicity and the like.
The purpose of the invention is realized by the following technical scheme:
the bifunctional silicon amine curing agent (SA) adopted by the invention is prepared by the method comprising the following steps: the difunctional silicon amine curing agent (SA) is obtained by taking dibasic secondary amine (BSA) and alkyl chlorosilane (ASC) as raw materials and performing nucleophilic substitution reaction under the action of alkali. The reaction formula is as follows:
Wherein, the structural formula of the diamine BSA is shown in the specification
Represents the connection mode of N atoms of two diamine, and the connection mode can be a single-chain connection plus methyl or a connection mode through a double aliphatic chain. Further, the secondary diamines may be secondary alicyclic amines, aliphatic amines and aromatic amines including piperazine, 1, 3-bis (4-piperidyl) propane, N '-dimethylethylenediamine, 4' -methylenebis (N-methylcyclohexan-1-amine), 4 '-methylenebis (N, 2-dimethylcyclohex-1-amine), 4' -methylenebis (N-methylaniline).
In the structural formula of Alkylchlorosilane (ASC), R groups are methyl, tert-butyl and phenyl respectively. Further, the alkylchlorosilane may be aliphatic chlorosilane, aromatic chlorosilane, etc., including trimethylchlorosilane, t-butyldimethylchlorosilane, phenyldimethylchlorosilane.
The base may be a tertiary aliphatic amine, a metal alkyl compound, etc., including Triethylamine (TEA), triethylenediamine (DABCO), 1, 8-diazabicycloundecen-7-ene (DBU), n-butyllithium (n-BuLi).
The method comprises the following steps: the reaction molar ratio of the raw material of the diamine, the alkyl chlorosilane and the alkali is 1: 2-4, and the preferable ratio is 1: 2.2; the reaction temperature for the nucleophilic substitution reaction is-78 ℃ to 40 ℃, preferably-78 ℃ and 40 ℃. The reaction solvent for nucleophilic substitution reaction may be dichloromethane, 1, 2-dichloroethane, diethyl ether, tetrahydrofuran, etc., and preferred solvents are dichloromethane and tetrahydrofuran.
The method also comprises the following separation and purification steps: and after the nucleophilic substitution reaction is finished, distilling or distilling under reduced pressure to remove the solvent, adding n-pentane to disperse and dissolve unreacted chlorosilane and the product of the silicon amine, filtering the n-pentane solution by using dried diatomite to remove insoluble salt and diamine, and distilling or distilling the filtrate under reduced pressure to remove the chlorosilane to obtain the high-purity target product.
Preferably, the bifunctional silicon amine curing agent comprises:
and (2) alicyclic bifunctional silicon amine curing agent: n, N ' -bis (trimethylsilyl) piperazine (SA1), N ' -bis (tert-butyldimethylsilyl) piperazine (SA2), N ' -bis (phenyldimethylsilyl) piperazine (SA3), 1, 3-bis (1- (trimethylsilyl) piperidin-4-yl) propane (SA4), 1, 3-bis (1- (tert-butyldimethylsilyl) piperidin-4-yl) propane (SA5), 1, 3-bis (1- (phenyldimethylsilyl) piperidin-4-yl) propane (SA 6);
fatty type bifunctional silicon amine curing agent: n, N ' -dimethyl-N, N ' -bis (trimethylsilyl) ethylenediamine (SA7), N ' -dimethyl-N, N ' -bis (tert-butyldimethylsilyl) ethylenediamine (SA8), N ' -dimethyl-N, N ' -bis (phenyldimethylsilyl) ethylenediamine (SA9), 4' -methylenebis (N-methyl-N-trimethylsilyl-cyclohex-1-amine) (SA10), 4' -methylenebis (N-methyl-N-tert-butyldimethylsilyl-cyclohex-1-amine) (SA11), 4' -methylenebis (N-methyl-N-phenyldimethylsilyl-cyclohex-1-amine) (SA12), 4,4' -methylenebis (N, 2-dimethyl-N-trimethylsilyl-cyclohex-1-amine) (SA13), 4' -methylenebis (N, 2-dimethyl-N-tert-butyldimethylsilyl-cyclohex-1-amine) (SA14), 4' -methylenebis (N, 2-dimethyl-N-phenyldimethylsilyl-cyclohex-1-amine) (SA 15);
Aromatic bifunctional silicon amine curing agent: 4,4' -methylenebis (N-methyl-N-trimethylsilyl-aniline) (SA16), 4' -methylenebis (N-methyl-N-tert-butyldimethylsilyl-aniline) (SA17), 4' -methylenebis (N-methyl-N-phenyldimethylsilyl-aniline) (SA 18).
The preparation method of the low dielectric silicon amine-epoxy resin copolymer provided by the invention comprises the following steps: the difunctional silicon amine curing agent and the epoxy resin are subjected to ring-opening polymerization under the action of a Lewis acid catalyst to obtain the low-dielectric silicon amine-epoxy resin copolymer.
In the preparation method of the low dielectric silicone amine-epoxy resin copolymer, the epoxy resin can be bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 4221 epoxy resin and the like; the Lewis acid catalyst may be a metal salt, such as ZnCl2、AlCl3、Mg(ClO4)2、LiBr、Bi(OSO2CF3)3、LiClO4Etc.; the ring-opening polymerization may be carried out by solution polymerization, and the solvent used may be DMF, THF, N-methylpyrrolidone or the like, or a solid may be directly obtained by bulk polymerization. Preferably, the epoxy resin is bisphenol A diglycidyl ether (BADGE) and the Lewis acid catalyst is Mg (ClO)4)2The solvent is THF.
A low dielectric silicone amine-epoxy resin copolymer is obtained by the preparation method.
Compared with the prior art, the invention has the following advantages and effects:
the invention adopts the difunctional silicon amine curing agent which can be subjected to ring-opening copolymerization and silicon-based migration with the epoxy resin under the catalysis of Lewis acid to obtain the silicon amine-epoxy copolymer without high-polarity hydroxyl and generated by active hydrogen-containing amino groups. The copolymer has excellent comprehensive performance such as low dielectric property, mechanical property, thermal stability, hydrophobicity and the like.
Drawings
FIG. 1 shows the dielectric properties, dielectric constant ε (left diagram) and dielectric loss tan δ (right diagram) of the polymers PSAE5, PSAE8 and PSAE17 in the frequency range of 20Hz to 30 MHz.
FIG. 2 shows the dielectric properties, dielectric constant ε (left diagram) and dielectric loss tan δ (right diagram) of the polymers PSAE5, PSAE8 and PSAE17 in the frequency range of 1-18 GHz.
Fig. 3 is a plot of nanoindentation load-depth curves (left panel), hardness, and modulus (right panel) for polymers PSAE5, PSAE8, and PSAE 17.
Fig. 4 is a plot of the glass transition temperature (left panel) and thermogravimetric analysis (right panel) of polymers PSAE5, PSAE8, and PSAE 17.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
EXAMPLE 1 Synthesis of alicyclic type bifunctional silicon amine curing agent
In N2In a dry 250mL three-necked flask, alicyclic diamine (50mmol), triethylamine (110mmol) and 70mL of anhydrous CH were added under an atmosphere2Cl2Stirring in ice bath for 10min to obtain chlorosilane (110mmol) in CH2Cl2And (50mL) slowly adding the solution dropwise, continuing stirring in an ice bath for reaction for 30min after the dropwise adding is finished, removing the ice bath, slowly raising the temperature to 40 ℃, and reacting for 12 h. After the reaction was completed, the solvent CH was distilled off2Cl2Adding a proper amount of dry n-pentane (100mL) into the residue, stirring and dispersing for 30min, and precipitating insoluble diamine raw materials such as insoluble triethylamine hydrochloride and the like; filtering the mixture by using dried diatomite, and distilling the filtrate to remove n-pentane to obtain the target product.
(1) According to the method, alicyclic diamine is selected from piperazine, chlorosilane is selected from trimethylchlorosilane, and finally the target product N, N' -bis (trimethyl silane) is obtainedSilyl) piperazine (SA1), 9.57g as a colorless transparent liquid, yield 83%.1H NMR(400MHz,CDCl3)δ2.70(s,8H),0.03(s,18H).13C NMR(101MHz,CDCl3)δ46.61(s),1.89(s).13C NMR(101MHz,CDCl3)δ46.82(s),-1.01(s).ESI-MS(M+)cal.for[C10H26N2Si2 +]230.16,found 230.20.
(2) According to the method, the alicyclic diamine is piperazine, the chlorosilane is tert-butyldimethylsilyl chlorosilane, and finally the target product N, N' -di (tert-butyldimethylsilyl) piperazine (SA2) is obtained, wherein the yield is 81%, and the white solid or colorless transparent needle-shaped crystal is 12.75 g.1H NMR(400MHz,CDCl3)δ2.74(s,8H),0.84(s,18H),0.00(s,12H).13C NMR(101MHz,CDCl3)δ48.45(s),26.92(s),25.81(s),20.57(s),-5.71(s).ESI-MS(M+)cal.for[C16H38N2Si2 +]314.25,found 314.26.
(3) According to the method, alicyclic diamine is piperazine, chlorosilane is phenyl dimethylchlorosilane, and finally the target product N, N' -bis (phenyl dimethylsilyl) piperazine (SA3) is obtained, wherein the yield is 78%, and the colorless transparent liquid is 13.84 g. 1H NMR(400MHz,CDCl3)δ7.56–7.52(m,4H),7.42–7.30(m,6H),2.91–2.68(m,8H),0.36–0.24(m,12H).13CNMR(101MHz,CDCl3)δ139.67(s),133.98(s),133.13(s),129.06(s),127.77(s),47.19(s),-2.12(s).ESI-MS(M+)cal.for[C20H30N2Si2 +]354.19,found 354.26.
(4) According to the method, alicyclic diamine is selected from 1, 3-bis (4-piperidyl) propane, chlorosilane is selected from trimethylchlorosilane, and finally the target product 1, 3-bis (1- (trimethylsilyl) piperidin-4-yl) propane (SA4) is obtained, wherein the yield is 83 percent, and the brown or yellow solid is 14.74 g.1H NMR(400MHz,CDCl3)δ3.09(d,J＝12.5Hz,4H),2.49(dd,J＝18.0,6.7Hz,4H),1.55(d,J＝11.4Hz,4H),1.39–1.00(m,10H),0.91(dd,J＝11.9,3.5Hz,2H),0.02(s,12H).13C NMR(101MHz,CDCl3)δ46.07(s),37.84(s),36.93(s),34.54(s),23.33(s),-0.74(s).ESI-MS(M+)cal.for[C19H42N2Si2 +]354.29,found 354.26.
(5) According to the method, alicyclic diamine is selected from 1, 3-bis (4-piperidyl) propane, chlorosilane is selected from tert-butyldimethylchlorosilane, and finally the target product 1, 3-bis (1- (tert-butyldimethylsilyl) piperidin-4-yl) propane (SA5) is obtained, wherein 17.58g of light brown solid or needle-shaped crystal is obtained, and the yield is 80%.1H NMR(400MHz,CDCl3)δ3.12(d,J＝12.7Hz,4H),2.58(t,J＝12.2Hz,4H),1.52(d,J＝11.9Hz,4H),1.27(d,J＝4.9Hz,4H),1.19–1.09(m,4H),0.90–0.81(m,22H),0.00(s,12H).13C NMR(101MHz,CDCl3)δ47.26(s),37.94(s),37.03(s),35.02(s),26.93(s),25.85(s),23.34(s),20.59(s),-5.50(s).ESI-MS(M+)Cal.for[C25H54N2Si2 +]438.38,found 438.30.
(6) According to the method, alicyclic diamine is selected from 1, 3-bis (4-piperidyl) propane, chlorosilane is selected from phenyldimethylchlorosilane, and finally the target product 1, 3-bis (1- (phenyldimethylsilyl) piperidin-4-yl) propane (SA6) is obtained, wherein the yield is 75 percent, and the light brown solid is 16.48 g.1H NMR(400MHz,CDCl3)δ7.54(dd,J＝7.4,2.0Hz,4H),7.39–7.34(m,6H),3.03(d,J＝12.2Hz,3H),2.64–2.46(m,5H),1.64(d,J＝12.7Hz,4H),1.28(dd,J＝12.9,6.9Hz,4H),1.12(ddd,J＝15.7,13.1,5.1Hz,8H),0.33(s,12H).13C NMR(101MHz,CDCl3)δ139.97(s),133.14(s),129.38(s),127.90(d,J＝12.2Hz),46.85(s),36.33(s),33.70(s),23.48(s),0.99(s).ESI-MS(M+)Cal.for[C29H46N2Si2 +]478.32,found 478.26.
EXAMPLE 2 Synthesis of aliphatic bifunctional Silicone amine curing Agents
N2Adding aliphatic diamine (30mmol) and 50mL of anhydrous THF into a dry 250mL three-neck flask under the atmosphere, cooling to-78 ℃, slowly adding n-butyllithium (2.5mol/L, hexane solution, 26.4mL) and 50mL of anhydrous THF, stirring for reaction for 30min, slowly dropwise adding a THF (30mL) solution of chlorosilane (110.0mmol), after dropwise adding, continuously stirring for reaction for 30min at-78 ℃, and then cooling to Reacting for 12h at-40 ℃. After the reaction is finished, the solvent THF is removed by distillation under reduced pressure, a proper amount of dry n-pentane (100mL) is added into the residue, stirring and dispersing are carried out for 30min, insoluble lithium salt and the like are precipitated, the obtained product is filtered by dry diatomite, and the n-pentane is removed from the filtrate by distillation, so that the target product is obtained.
(1) According to the method, the aliphatic diamine is N, N ' -dimethylethylenediamine, the chlorosilane is trimethylchlorosilane, and finally the target product N, N ' -dimethyl-N, N ' -bis (trimethylsilyl) ethylenediamine (SA7) is obtained, wherein the yield is 84 percent, and the colorless transparent liquid is 9.78 g.1H NMR(400MHz,CDCl3)δ2.68(s,4H),2.46(s,6H),0.03(s,18H).13C NMR(101MHz,CDCl3)δ50.07(s),35.20(s),-0.62(s).ESI-MS(M+)cal.for[C10H28N2Si2 +]232.18,found 232.13.
(2) According to the method, the aliphatic diamine is N, N ' -dimethylethylenediamine, the chlorosilane is tert-butyldimethylsilyl chloride, and finally the target product N, N ' -dimethyl-N, N ' -di (tert-butyldimethylsilyl) ethylenediamine (SA8) is obtained, wherein the yield is 81 percent, and the colorless transparent needle-shaped crystal is 12.83 g.1H NMR(400MHz,CDCl3)δ2.74(s,4H),2.53(s,6H),0.86(s,18H),0.03(s,12H).13C NMR(101MHz,CDCl3)δ50.92(s),36.56(s),27.17(s),20.84(s),-5.15(s).ESI-MS(M+)cal.for[C16H40N2Si2 +]316.26,found 316.27.
(3) According to the method, the aliphatic diamine is N, N ' -dimethylethylenediamine, the chlorosilane is phenyldimethylchlorosilane, and finally the target product of N, N ' -dimethyl-N, N ' -bis (phenyldimethylsilyl) ethylenediamine (SA9) is obtained, wherein the yield is 76 percent, and the colorless transparent liquid is 13.56 g.1H NMR(400MHz,CDCl3)δ7.54(d,J＝6.2Hz,4H),7.35–7.32(m,6H),2.69(s,4H),2.44(s,6H),0.27(s,12H).13C NMR(101MHz,CDCl3)δ139.95(s),133.77(s),133.13(s),129.38(s),127.83(s),51.61(s),36.67(s),-1.88(s).ESI-MS(M+)cal.for[C20H32N2Si2 +]356.21,found 356.16.
(4) According to the method, the aliphatic diamine is 4,4 '-methylenebis (N-methylcyclohex-1-amine) and the chlorosilane is trimethylchlorosilane, and finally the target product, namely 4,4' -methylenebis (N-methyl-N-trimethylsilyl-cyclohex-1-amine) (SA10) is obtained, the yield is 80%, and the yield is 9.18 g. 1H NMR(400MHz,CDCl3)δ2.69–2.49(m,2H),2.38(d,J＝11.3Hz,6H),1.77–1.62(m,4H),1.58–1.37(m,10H),1.30–1.15(m,6H),0.02(d,J＝16.1Hz,18H).13C NMR(101MHz,CDCl3)δ59.17(s),34.07(s),33.32(s),32.32(s),29.22(s),28.07(s),-0.03(d,J＝2.8Hz).ESI-MS(M+)cal.for[C21H46N2Si2 +]382.32,found 382.30.
(5) According to the method, the aliphatic diamine is 4,4 '-methylenebis (N-methylcyclohex-1-amine) and the chlorosilane is tert-butyldimethylsilyl chloride, and finally the target product, namely 4,4' -methylenebis (N-methyl-N-tert-butyldimethylsilyl-cyclohex-1-amine) (SA11) is obtained, 11.62g of light brown needle crystals are obtained, and the yield is 83%.1H NMR(400MHz,CDCl3)δ2.76–2.56(m,2H),2.44–2.37(m,6H),1.75(d,J＝12.5Hz,4H),1.65–1.42(m,12H),1.24(dd,J＝21.4,8.0Hz,4H),0.87(s,18H),0.05(s,12H).13C NMR(101MHz,CDCl3)δ55.98(s),34.57(s),34.07(s),33.32(s),32.32(s),31.50(s),30.18(s),29.22(s),28.07(s),-0.05(s).ESI-MS(M+)cal.for[C27H58N2Si2 +]466.41,found 466.36.
(6) According to the method, the aliphatic diamine is 4,4 '-methylenebis (N-methylcyclohex-1-amine) and the chlorosilane is phenyldimethylchlorosilane, and finally the target product, namely 4,4' -methylenebis (N-methyl-N-phenyldimethylsilyl-cyclohex-1-amine) (SA12) is obtained, and the yield is 81%, and the yellow oily liquid is 12.57 g.1H NMR(400MHz,CDCl3)δ7.56–7.51(m,4H),7.36–7.32(m,6H),2.78–2.64(m,1H),2.54(d,J＝3.9Hz,1H),2.38(d,J＝8.6Hz,6H),1.71(d,J＝8.4Hz,4H),1.58-1.41(m,10H),1.26(d,J＝5.9Hz,6H),0.31(d,J＝14.1Hz,12H).13C NMR(101MHz,CDCl3)140.94(s),133.83(s),129.37(s),127.82(s),55.93(s),38.14(s),34.02(s),33.28(s),32.30(s),29.17(s),28.07(s),0.98(s).ESI-MS(M+)cal.for[C31H50N2Si2 +]506.35,found 506.43.
(7) According to the method, the aliphatic diamine is 4,4 '-methylenebis (N, 2-dimethylcyclohex-1-amine) and the chlorosilane is trimethylchlorosilane, and finally the target product, namely 4,4' -methylenebis (N, 2-dimethyl-N-trimethylsilyl-cyclohex-1-amine) (SA13) is obtained, and the yield is 79 percent, wherein the yellow oily liquid is 9.74 g.1H NMR(400MHz,CDCl3)δ2.46(d,J＝12.9Hz,1H),2.34–2.22(m,7H),1.64(ddd,J＝26.2,17.7,10.0Hz,8H),1.35(ddd,J＝10.5,9.9,3.0Hz,5H),1.07–0.90(m,5H),0.83(d,J＝6.4Hz,6H),0.64(d,J＝11.9Hz,2H),0.05(s,18H).13CNMR(101MHz,CDCl3)δ61.24(s),44.90(s),42.38(s),42.27(s),34.57(s),33.60(s),33.50(s),31.34(s),27.06(s),19.73(s),0.09(s).ESI-MS(M+)cal.for[C23H50N2Si2 +]410.35,found 410.36.
(8) According to the method, the aliphatic diamine selects 4,4 '-methylenebis (N, 2-dimethylcyclohex-1-amine) and the chlorosilane selects tert-butyldimethylchlorosilane, and finally the target product, namely 4,4' -methylenebis (N, 2-dimethyl-N-tert-butyldimethylsilyl-cyclohex-1-amine) (SA14) is obtained, wherein the yield is 78 percent, and the weight of the product is 11.58 g. 1H NMR(400MHz,CDCl3)δ2.42–2.19(m,8H),1.72–1.50(m,8H),1.28(s,2H),0.97–0.80(m,30H),0.60(dd,J＝24.9,12.8Hz,2H),0.02(d,J＝10.2Hz,12H).13C NMR(101MHz,CDCl3)δ61.60(s),44.88(s),42.40(d,J＝12.3Hz),34.74(s),33.65(s),31.51(s),28.43(s),27.25(s),20.43(s),19.76(s),-4.57(s),-5.16(s).ESI-MS(M+)cal.for[C29H62N2Si2 +]494.44,found 494.40.
(9) According to the method, the aliphatic diamine selects 4,4 '-methylenebis (N, 2-dimethylcyclohex-1-amine) and the chlorosilane selects phenyldimethylchlorosilane, and finally the target product, namely 4,4' -methylenebis (N, 2-dimethyl-N-phenyldimethylsilyl-cyclohex-1-amine) (SA15) is obtained, 12.19g of yellow oily liquid is obtained,the yield thereof was found to be 76%.1H NMR(400MHz,CDCl3)δ7.60(dd,J＝6.6,2.6Hz,4H),7.41–7.38(m,6H),2.34(s,8H),1.83–1.59(m,8H),1.42(ddd,J＝20.5,13.1,3.7Hz,8H),1.05–0.99(m,2H),0.91–0.87(m,6H),0.64(d,J＝11.7Hz,2H),0.36–0.30(m,12H).13C NMR(101MHz,CDCl3)δ140.72(s),133.99(s),128.83(s),127.69(s),61.37(s),44.80(s),42.26(s),34.60(s),33.68(s),31.38(s),27.61(s),26.70(s),26.24(s),19.80(s),15.57(s),13.90(s),-1.28(s),-1.50(s).ESI-MS(M+)cal.for[C33H54N2Si2 +]534.38found 534.44.
EXAMPLE 3 Synthesis of aromatic bifunctional Silamine curing agent
N2In a dry 250mL three-necked flask under an atmosphere, adding aromatic diamine (30mmol) and anhydrous THF (50 mL), cooling to-78 ℃, slowly adding n-butyllithium (2.5mol/L, hexane solution, 26.4mL) and anhydrous THF (50 mL), stirring for reaction for 30min, slowly adding a THF (30mL) solution of chlorosilane (66mmol), after the dropwise addition, continuously stirring for reaction for 30min at-78 ℃, and then reacting for 12h at-40 ℃. After the reaction is finished, the solvent THF is removed by distillation under reduced pressure, a proper amount of dry n-pentane (100mL) is added into the residue, stirring and dispersing are carried out for 30min, insoluble lithium salt and the like are precipitated, the obtained product is filtered by dry diatomite, and the n-pentane is removed from the filtrate by distillation, so that the target product is obtained.
(1) According to the method, 4 '-methylenebis (N-methylaniline) is selected as the aromatic diamine, trimethylchlorosilane is selected as the chlorosilane, and finally the target product, namely 4,4' -methylenebis (N-methyl-N-trimethylsilyl-aniline) (SA16) is obtained, wherein 8.67g of yellow oily liquid is obtained, and the yield is 78%. 1H NMR(400MHz,CDCl3)δ7.02(t,J＝5.7Hz,4H),6.83–6.77(m,4H),3.81(s,2H),2.87(s,6H),0.25(s,18H).13C NMR(101MHz,CDCl3)δ149.00(s),129.14(s),117.84(s),112.69(s),40.23(s),35.34(s),0.85(s).ESI-MS(M+)cal.for[C21H34N2Si2 +]370.23,found 370.31.
(2) According to the method, the aromatic diamine is selected from 4,4' -methylene bis (N-methylaniline) and chlorineThe silane was tert-butyldimethylsilyl chloride, and the desired product, 4' -methylenebis (N-methyl-N-tert-butyldimethylsilyl-aniline) (SA17), was obtained in the form of a yellow solid (10.10 g) with a yield of 74%.1H NMR(400MHz,CDCl3)δ7.00(d,J＝8.2Hz,4H),6.54(d,J＝8.2Hz,4H),3.77(s,2H),2.79(d,J＝5.4Hz,6H),0.90(s,18H),0.08(s,12H).13CNMR(101MHz,CDCl3)δ147.54(s),131.02(s),129.64(s),112.71(s),40.20(s),31.13(s),25.77(s),18.10(s),-3.47(s).ESI-MS(M+)cal.for[C27H46N2Si2 +]454.33,found 454.39.
(3) According to the method, 4 '-methylenebis (N-methylaniline) is selected as the aromatic diamine, phenyldimethylchlorosilane is selected as the chlorosilane, and finally the target product, namely 4,4' -methylenebis (N-methyl-N-phenyldimethylsilyl-aniline) (SA18) is obtained, wherein 11.27g of yellow solid is obtained, and the yield is 69%.1H NMR(600MHz,CDCl3)δ7.53(d,J＝5.4Hz,4H),7.34(d,J＝5.1Hz,6H),6.95(d,J＝8.1Hz,4H),6.78(d,J＝8.2Hz,4H),3.75(s,2H),2.96(s,6H),0.47(s,12H).13C NMR(101MHz,CDCl3)δ148.68(s),139.36(s),133.67(s),129.31(s),129.06(s),128.07(s),118.18(s),112.68(s),40.23(s),35.97(s),-0.35(s).ESI-MS(M+)cal.for[C31H38N2Si2 +]494.26,found 494.20.
The bifunctional silicon amine curing agent obtained in the above embodiments 1 to 3 can be copolymerized with various epoxy resins to form a silicon amine-epoxy copolymer. The following is an example of copolymerization of three different types of silamines, such as alicyclic type silamine, aliphatic type silamine, and aromatic type silamine, with bisphenol A diglycidyl ether (BADGE) to obtain a silamine-epoxy copolymer and its performance characterization.
Example 4 Synthesis of alicyclic type Silicone amine-epoxy copolymer PSAE5
N2In a dry 100mL three-neck flask under the atmosphere, adding bisphenol A diglycidyl ether (BADGE, 30mmol), alicyclic type silicon amine SA5(30mmol), anhydrous magnesium perchlorate (0.9mmol) and 100mL anhydrous THF, and heating to reflux for 36 h; cooling the reaction system to room temperature, centrifuging, and removing insoluble components Dividing; pouring the supernatant into methanol to obtain polymer precipitate, dissolving the polymer precipitate in THF, and repeating the methanol precipitation twice; the residual solvent was removed under vacuum at room temperature to give polymer PSAE5, or dissolved in THF to make a solution for use. Polymerization conversion of 90%, polymer molecular weight: the number average molecular weight Mn is 13.7kDa, the weight average molecular weight Mw is 19.0kDa, and PDI is 1.33.
Example 5 Synthesis of aliphatic Silamine-epoxy copolymer PSAE8
N2In a dry 100mL three-neck flask under the atmosphere, adding bisphenol A diglycidyl ether (BADGE, 30mmol), alicyclic type silicon amine SA8(30mmol), anhydrous magnesium perchlorate (0.9mmol) and 100mL anhydrous THF, and heating to reflux for 36 h; cooling the reaction system to room temperature, centrifuging, and removing insoluble components; pouring the supernatant into methanol to obtain polymer precipitate, dissolving the polymer precipitate in THF, and repeating the methanol precipitation twice; the residual solvent was removed under vacuum at room temperature to give polymer PSAE8, or dissolved in THF to make a solution for use. Polymerization conversion 84%, polymer molecular weight: the number average molecular weight Mn is 10.7kDa, the weight average molecular weight Mw is 14.2kDa, and PDI is 1.38.
EXAMPLE 6 Synthesis of aromatic type Silamine-epoxy copolymer PSAE17
A dry 100mL three-necked flask equipped with a magneton and a condenser was charged with bisphenol A diglycidyl ether (BADGE, 30mmol), alicyclic type silicon amine SA17(30mmol) and anhydrous magnesium perchlorate (0.9mmol), followed by vacuum evacuation and N charge2(cycle 3 times). Adding 100mL of anhydrous THF through an injector, and heating a mixed system to reflux; reacting for 36h, cooling the reaction system to room temperature, centrifuging, and removing insoluble components; pouring the supernatant into methanol to obtain polymer precipitate, dissolving the polymer precipitate in THF, and repeating the methanol precipitation twice; the residual solvent was removed under vacuum at room temperature to give polymer PSAE17, or dissolved in THF to make a solution for use. Polymerization conversion 73%, polymer molecular weight: the number average molecular weight Mn is 6.9kDa, the weight average molecular weight Mw is 9.2kDa, and the PDI is 1.38.
Example 7 dielectric Properties of representative Silamine-epoxy copolymers
The prepared polymer solution (concentration about 20mg/mL) was poured into a corresponding polytetrafluoroethylene mold, wherein the mold size for the low frequency range test was a disk with a diameter of 45mm and a depth of 2mm, and the mold size for the high frequency test was a coaxial ring with an outer/inner diameter of 7/3mm and a thickness of 2 mm; and after the solvent is completely volatilized, drying for 12 hours in vacuum at the temperature of 30 ℃ to obtain a polymer test sample. The dielectric property of the dielectric material in the low-frequency range of 20Hz to 30MHz is measured by adopting an impedance analyzer Keysight E4990A, and the dielectric property in the high-frequency range of 1 to 18GHz is measured by a vector network analyzer. The test results show that the polymer shows excellent dielectric properties in both low-frequency and high-frequency ranges, the dielectric constant epsilon of the polymer is between 2.1 and 2.5, the dielectric loss tan delta is in the range of 0.006 to 0.02, and the test results of the representative silicon amine-epoxy copolymer are shown in the table 1 and attached figures 1 and 2.
TABLE 1 dielectric Properties of representative Silamine-epoxy copolymers
Example 8 mechanical Properties of representative Silamine-epoxy copolymers
The polymer was prepared into a sheet, the mechanical properties thereof were measured using a nanoindenter (Anton Paar UNHT noninduction tester, Switzerland), the peak value of indentation load was 10mN, a load-displacement curve was measured, and the hardness and elastic modulus were obtained by calculation, the results of which are shown in Table 2 and FIG. 3.
TABLE 2 mechanical Properties of representative Silamine-epoxy copolymers
| Numbering | Polymer and method of making same | Hardness (GPa) | Modulus of elasticity (GPa) |
| 1 | PSAE5 | 0.165±0.001 | 2.663±0.10 |
| 2 | PSAE8 | 0.226±0.017 | 3.998±0.19 |
| 3 | PSAE17 | 0.176±0.009 | 3.285±0.27 |
Example 9 glass transition temperature, thermal stability and surface wettability of representative Silamine-epoxy copolymers
Glass transition temperature (T) of polymerg) Measured by a Perkin Elmer DSC8500 differential scanning calorimeter, the test conditions are as follows: n is a radical of2The testing temperature range of the atmosphere is-50 ℃ to 100 ℃, and the heating rate is 10 ℃/min. The thermal stability of the polymers was tested using a TA Instruments Q500 thermogravimetric analyzer under the following test conditions: n is a radical of2The atmosphere, the gas flow rate is 40mL/min, the testing temperature range is room temperature-600 ℃, and the heating rate is 10 ℃/min. Polymer surface wettability was measured by means of a video contact angle meter (OCA20, Dataphysic) by dropping a 3 μ L volume drop of water on the polymer surface, measuring the drop contact angle after it had equilibrated for 10s, measuring five times at different locations and averaging to give the reported value. The glass transition temperature (T) was measured g) 10% weight loss temperature (T)10％) The carbon residue (Char yield) and the Water Contact Angle (WCA) are shown in the table3 and fig. 4.
TABLE 3 glass transition temperature and thermal stability of representative Silamine-epoxy copolymers
| Numbering | Polymer and method of making same | Tg(℃) | T10％(℃) | Char yield(％) | WCA(°) |
| 1 | PSAE5 | 43.8 | 321 | 13.7 | 101.7±3.8 |
| 2 | PSAE8 | 45.1 | 310 | 19.6 | 94.9±4.2 |
| 3 | PSAE17 | 31.2 | 309 | 25.5 | 104.7±0.9 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a low dielectric silicon amine-epoxy resin copolymer is characterized by comprising the following steps: the difunctional silicon amine curing agent and the epoxy resin are subjected to ring-opening polymerization under the action of a Lewis acid catalyst to obtain a silicon amine-epoxy resin copolymer;
the difunctional silicon amine curing agent is prepared by the method comprising the following steps: using binary secondary amine and alkyl chlorosilane as raw materials, and obtaining the difunctional silicon amine curing agent through nucleophilic substitution reaction under the action of alkali; the reaction molar ratio of the raw material of the diamine, the alkyl chlorosilane and the alkali is 1: 2-4.
2. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by: the difunctional silicon amine curing agent comprises: N,N’-bis (trimethylsilyl) piperazine,N,N’Di (tert-butyldimethylsilyl) piperazine,N,N’Bis (phenyldimethylsilyl) piperazine, 1, 3-bis (1- (trimethylsilyl) piperidin-4-yl) propane, 1, 3-bis (1- (tert-butyldimethylsilyl) piperidin-4-yl) propane, 1, 3-bis (1- (phenyldimethylsilyl) piperidin-4-yl) propane, and mixtures thereof,N,N’-dimethyl-N,N’Bis (trimethylsilyl) ethylenediamine,N,N’-dimethyl-N,N’Di (tert-butyldimethylsilyl) ethylenediamine,N,N’-dimethyl-N,N’Bis (phenyldimethylsilyl) ethylenediamine, 4' -methylenebis (A)N-methyl-NTrimethylsilyl-cyclohex-1-amine), 4' -methylenebis (b-methylene-bis (b-cyclohexylmethyl-1-amine)N-methyl-N-tert-butyldimethylsilyl-cyclohex-1-amine), 4' -methylenebis (b-methylene-bis: (b-butyl-dimethylsilyl-cyclohex-1-amine)N-methyl-N-phenyldimethylsilyl-cyclohex-1-amine), 4' -methylenebis (b-methyl-ethyl-phenyl-methyl-amino-1-amine)N2-dimethyl-NTrimethylsilyl-cyclohex-1-amine), 4' -methylenebis (b-methylene-bis (b-cyclohexylmethyl-1-amine)N2-dimethyl-N-tert-butyldimethylsilyl-cyclohex-1-amine), 4' -methylenebis (b-methylene-bis: (b-butyl-dimethylsilyl-cyclohex-1-amine)N2-dimethyl-N-phenyldimethylsilyl-cyclohex-1-amine), 4' -methylenebis (b-methyl-ethyl-phenyl-methyl-amino-1-amine)N-methyl-N-trimethylsilyl-aniline), 4' -methylenebis (m-ethyl-methyl-N-trimethylsilyl-aniline)N-methyl-N-tert-butyldimethylsilyl-aniline), 4' -methylenebis (N-methyl-N-ethyl-N-methyl-phenyl-N-methyl-phenyl-N-phenyl-methyl-phenyl-methyl-ethyl-phenyl-methyl-phenyl-methyl-ethyl-phenyl-methyl-phenyl-ethyl-methyl-phenyl-methyl-ethyl-phenyl-ethyl-methyl-ethyl-methyl-phenyl-ethyl-phenyl-methyl-ethyl-phenyl-ethyl-methyl-ethyl-methyl-ethyl-phenyl-methyl-ethyl-methyl-phenyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl N-methyl-N-phenyl dimethylsilyl-aniline).
3. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by: the epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and 4221 epoxy resin.
4. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by: the Lewis acid catalyst comprises ZnCl2、AlCl3、Mg(ClO4)2、LiBr、Bi(OSO2CF3)3、LiClO4。
5. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by: the ring-opening polymerization adopts a solution polymerization or bulk polymerization mode; the solvent used in the solution polymerization includes DMF, THF,N-methyl pyrrolidone.
6. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by:
the dibasic secondary amine comprises alicyclic amine, aliphatic amine and aromatic amine;
the alkyl chlorosilane comprises aliphatic chlorosilane and aromatic chlorosilane;
the alkali comprises tertiary aliphatic amine and metal alkyl compound.
7. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by:
The dibasic secondary amine comprises piperazine, 1, 3-bis (4-piperidyl) propane and 4,4' -methylenebis (piperidine)NMethylcyclohex-1-amine), 4' -methylenebis (N-methyl-L-amino)N2-dimethylcyclohex-1-amine), 4' -methylenebis (A)N-methylaniline);
the alkyl chlorosilane comprises trimethyl chlorosilane, tert-butyl dimethyl chlorosilane and phenyl dimethyl chlorosilane;
the alkali comprises triethylamine, triethylene diamine, 1, 8-diazabicycloundecen-7-ene and n-butyllithium.
8. The method of claim 1, wherein the low dielectric siloxane-epoxy copolymer is prepared by:
the reaction temperature of the nucleophilic substitution reaction is-78 ℃ to 40 ℃;
the reaction solvent for nucleophilic substitution reaction includes dichloromethane, 1, 2-dichloroethane, diethyl ether and tetrahydrofuran.
9. A low dielectric silicone-epoxy copolymer characterized by: obtained by the production method according to any one of claims 1 to 8.
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